EP2537840B1 - Process to produce valerolactone from levulinic acid - Google Patents
Process to produce valerolactone from levulinic acid Download PDFInfo
- Publication number
- EP2537840B1 EP2537840B1 EP12172349.8A EP12172349A EP2537840B1 EP 2537840 B1 EP2537840 B1 EP 2537840B1 EP 12172349 A EP12172349 A EP 12172349A EP 2537840 B1 EP2537840 B1 EP 2537840B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reaction
- amount
- produced
- levulinic acid
- converting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Definitions
- the present invention relates to a process for the production of valerolactone.
- valerolactone (5-methylbutyrolactone, in the context of the invention also referred to as “valerolactone"
- adipic acid (1,6-hexanedioic acid) which is an important precursor for inter alia the production of polyamides such as polyamide 6,6 (also referred to as “Nylon”) or polyamide 4,6 (also referred to as "Stanyl”).
- esters of adipic acid may be used in plasticisers, lubricants, solvents and in a variety of polyurethane resins.
- Other uses of adipic acid are as food acidulants, applications in adhesives, insecticides, tanning and dyeing.
- adipic acid The most important process to produce adipic acid is based on oil and starts from benzene.
- a disadvantage of this process is that it is based on fossil derived oil and is therefore not renewable.
- Another disadvantage is the evolution of NOx during the oxidation step, which either is vented to the air, which is highly undesirable as it is a greenhouse gas, or its catalytically destroyed, which is an expensive process.
- a third production route to produce adipic acid involves the use of valerolactone which can be converted to methylpentenoates in the presence of an acidic or basic catalyst in the gas phase or in the liquid phase.
- Methylpentenoate can be converted to dimethyladipate in an alkoxycarbonylation reaction which dimethyladipate can be converted to adipic acid in a simple hydrolysis reaction.
- the use of valerolactone in the production of adipic acid is environmentally advantageous since it can be produced from levulinic acid, which in turn can be produced from renewable sources such as plant waste.
- US2003/0055270 discloses a process to produce valerolactone from levulinic acid using a solid Ru catalyst, e.g. supported on carbon.
- a problem of the process as described by US2003/0055270 is that the selectivity towards valerolactone is insufficient.
- Another problem of process as described by US2003/0055270 is that the conversion yield is insufficient.
- the use of valerolactone in the production of adipic acid is environmentally advantageous since it can be produced from levulinic acid, which in turn can be produced from renewable sources such as plant waste.
- the invention provides a process for the preparation of valerolactone, said process comprising reacting levulinic acid with hydrogen by using a solid Ru catalyst, characterised in that the process is carried out in the presence of at least 0.08 % (w/w) water relative to the amount of levulinic acid.
- the amount of water is expressed relative to the amount of initial levulinic acid, i.e. the amount of levulinic acid at the start of the process when no or hardly any levulinic acid has been converted.
- the amount of levulinic acid can be determined e.g. by GC.
- the process of the invention involves a hydrogenation reaction.
- the Ru catalyst is preferably present in a catalytic amount and is suitable for hydrogenation of ketones.
- the Ru catalyst is supported on a support medium, for example on carbon or alumina.
- Ru oxide RuO
- RuO can also be used.
- the conversion of levulinic acid to valerolactone using a solid Ru catalyst as carried out in US2003/0055270 is done without the addition of any water.
- the catalyst is dried at 400°C for 2 hours prior to the process.
- That reacting levulinic acid with hydrogen by using a solid Ru catalyst in the presence of at least 0.08% (w/w) water relative to the amount of levulinic acid results in high conversion yield and/or a high selectivity is all the more surprising since said reaction involves the production of condensation water. As the reaction proceeds, the amount of water in the process increases. Nevertheless, it appears that the condensation water which builds up during the course of the reaction does not impart the same effect with respect to reaction velocity and/or selectivity as does the initial presence of at least 0.08% w/w water, i.e. the initial presence of at least 0.08% w/w water in the process is essential.
- the amount of water in the process of the invention is preferably at least 0.1% w/w, more preferably at least 0.2%, at least 0.3%, at least 0.4% w/w, more preferably at least 0.5%, at least 0.75% w/w, more preferably at least 1%, at least 1.3%, at least 1.5% w/w, even more preferably at least 1,7%, at least 2%, at least 2.5% w/w, all relative to the amount of levulinic acid.
- the upper limit of the amount of water is less critical. However, if the amount of water is too high, the substrate and/or catalyst may be diluted such that the reaction velocity or productivity may decrease which is undesired.
- the amount of water in the process of the invention is preferably less than 10% w/w, more preferably less than 8% w/w, less than 6% w/w, less than 5% w/w, all relative to the amount of levulinic acid.
- the water which is present in the process of invention may be added separately, or added as part of one or more of the components, or both. For example, it may be added to the process in the form of liquid water or in the form of steam. It may also be present in the form of crystal water.
- the water may also be added to process together with one or more of the reaction components, e.g. as part of the levulinic acid or the Ru catalyst or both.
- the water may also be added first and the other reaction components are added later. Reaction components such as levulinic acid and the catalyst may also be added first, and the water may be added subsequently.
- the temperature at which the process of the invention is carried out is not critical and may be anywhere between 100 and 250°C, more preferably between 100 and 200°C. Preferably a temperature of between 100 and 150°C is used because it seems that the highest selectivity can be obtained in this temperature range. Lower temperatures are also desired due to cost considerations and equipment requirements.
- the pressure at which the process of the invention is carried out is also not critical, but it may be advantageous to carry out the process at lower pressure, e.g. less than 4.8 MPa.
- the pressure is between 1 and 4 MPa, more preferably between 1 and 3 MPa, even more preferably between 1 and 2.5 MPa, even more preferably between 1 and 2.2 MPa.
- the amount of catalyst to be used is not critical.
- the amount of catalyst is between 2.5 and 2,000 ppm Ru relative to the initial amount of levulinic acid present in the reaction mixture, i.e. the amount of levulinic acid which is present in the reaction mixture at the start of the reaction when no or hardly any levulinic acid has been converted. More preferably the amount of catalyst is between 5 and 1,000 ppm Ru, even more preferably between 10 and 500 ppm Ru, all relative to the initial amount of levulinic acid.
- the process of the invention may advantageously be done at low (e.g. less than 500 ppm Ru) catalyst concentrations whilst yielding good selectivity.
- the effect of at least 0.08% w/w water relative to the amount of levulinic acid may be stronger at lower amounts catalyst.
- the presence at least 0.08% w/w water relative to the amount of levulinic acid may be more important, and indeed may even be required for the hydrogenation reaction to proceed at all when a low amount of catalyst is selected, for instance for economic reasons.
- Ru catalysts such as Ru/C or Ru-Al 2 O 3 are commercially available and the amount of Ru and any support are usually labeled. In case the amount of Ru is not given, the skilled person knows how to determine the amount of Ru, for example by atomic absorption spectrometry or plasma emission spectrometry.
- the process of the invention may be carried in the absence of a solvent.
- a solvent is understood to be added to the reaction mixture, i.e. in the meaning of the invention the reaction product is not considered a solvent.
- the absence of a solvent may advantageously result in higher conversion and/or selectivity and may be preferred for economic reasons.
- the levulinic acid may be produced from renewable sources.
- a suitable example of renewable sources is plant material, particularly plant waste.
- Plant material usually contains carbohydrates that can serve as a starting molecule for the production of levulinic acid.
- levulinic acid can be prepared by converting a C6 carbohydrate to levulinic acid in an acid-catalysed reaction. Such processes are for example described in US3,065,263 ; B. Girisuta et al., Chem. Eng. Res. Des. 2006, 84, 339-349 ; B. F. M. Kuster et al., Carbohydr. Res., 1977, 54,165-176 ; WO89/10362 ; and WO96/40609 .
- C6 carbohydrates are glucose, fructose, mannose and galactose.
- Preferred raw material for the C6 carbohydrates is lignocellulosic material containing carbohydrate based polymers composed partly or entirely from C6 sugars such as lignocellulose, cellulose, starch and hemicellulose.
- the C6 carbohydrate may comprise other components, such as plant waste, sewage etc.
- the invention may be particularly useful since it allows for economically feasible production of valerolactone, and also of derivatives thereof such as methylpentenoate, adipic acid dimethylester, adipic acid, hexamethylenediamine, and polyamide 6,6, all produced via or from renewable sources.
- a suitable renewable source is plant material, which can be converted into levulinic acid.
- the process of US2003/0055270 suffers from low conversion yield (usually less than 100%, often even less than 80% and even as low as 32%), low selectivity (less than 98.5%, occasionally even as low as 67.7%), is done at high process temperature (215°C) and high pressure (4.8 MPa), makes use of a solvent (dioxane) and high catalyst concentrations.
- the amount of Ru/C used in Table 1 of US2003/0055270 typically ranges between 2% and 20% (w/w) relative to the amount of levulinic acid, which corresponds to a range of between approximately 1000 and 10,000 ppm Ru relative to the amount of levulinic acid, respectively.
- Low catalyst concentrations (such as for instance less than 1000 ppm Ru) are usually economically desirable, but the selectivity in the process as described in US2003/0055270 appears to be lower at lower catalyst concentrations. Said barriers can be overcome by the process of the invention.
- the invention further provides a process to produce methylpentenoate comprising converting valerolactone produced by the process of the invention into methylpentenoate by treatment with methanol in the presence of an acidic or basic catalyst.
- the conversion of valerolactone to methyl pentenoate can be done either in the liquid phase or in the gas phase, and is inter alia described in WO 2005/058793 , WO2004/007421 , and US4,740,613 .
- the invention also provides a process to prepare adipic acid dimethylester comprising converting methylpentenoate produced in the process of the invention by treatment with a catalyst, CO and methanol.
- a catalyst e.g., CO and methanol.
- Such an alkoxycarbonylation reaction is described by e.g. W02001/068583 .
- the invention also provides a process to prepare adipic acid comprising converting adipic acid dimethylester produced in the process of the invention to adipic acid in a hydrolysis reaction.
- the hydrolysis of adipic acid dimethylester to adipic acid is well known to the person skilled in the art.
- the hydrolysis is preferably catalysed by an acidic catalyst.
- the invention also provides a process to prepare ammonium adipate comprising converting adipic acid produced by the process of the invention to ammonium adipate by treatment with ammonia.
- the invention also provides a process to prepare adiponitrile comprising converting ammonium adipate produced in the process of the invention into adiponitrile in a dehydration reaction.
- the invention also provides a process to prepare hexamethylenediamine comprising converting adiponitrile produced of the process of the inventiont into hexamethylenediamine in a reduction reaction.
- the invention also provides a process to produce polyamide 6,6 by converting adipic acid, preferably adipic acid produced in a process according of the invention with hexamethylenediamine, preferably hexamethylenediamine produced by a process of the invention, in a polymerization reaction.
- Polyamide 6,6 produced by the invention particularly polyamide 6,6 produced from adipic acid and hexamethylenediamine produced by a process of the invention may be advantageously environmentally sustainable.
- Levulinic acid was obtained from Acros Organics, Geel, Belgium. Valerolactone was measured by GC analysis using cyclohexylbenzene as an external standard.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Polyamides (AREA)
- Furan Compounds (AREA)
Description
- The present invention relates to a process for the production of valerolactone.
- Gamma-valerolactone (5-methylbutyrolactone, in the context of the invention also referred to as "valerolactone") is a valuable compound which is inter alia used in the production of adipic acid (1,6-hexanedioic acid) which is an important precursor for inter alia the production of polyamides such as polyamide 6,6 (also referred to as "Nylon") or polyamide 4,6 (also referred to as "Stanyl"). Further, esters of adipic acid may be used in plasticisers, lubricants, solvents and in a variety of polyurethane resins. Other uses of adipic acid are as food acidulants, applications in adhesives, insecticides, tanning and dyeing.
- The most important process to produce adipic acid is based on oil and starts from benzene. A disadvantage of this process is that it is based on fossil derived oil and is therefore not renewable. Another disadvantage is the evolution of NOx during the oxidation step, which either is vented to the air, which is highly undesirable as it is a greenhouse gas, or its catalytically destroyed, which is an expensive process.
- New processes for the production of adipic acid have been developed based on butadiene. However, such processes are also environmentally unfavourable.
- A third production route to produce adipic acid involves the use of valerolactone which can be converted to methylpentenoates in the presence of an acidic or basic catalyst in the gas phase or in the liquid phase. Methylpentenoate can be converted to dimethyladipate in an alkoxycarbonylation reaction which dimethyladipate can be converted to adipic acid in a simple hydrolysis reaction. The use of valerolactone in the production of adipic acid is environmentally advantageous since it can be produced from levulinic acid, which in turn can be produced from renewable sources such as plant waste.
-
US2003/0055270 discloses a process to produce valerolactone from levulinic acid using a solid Ru catalyst, e.g. supported on carbon. A problem of the process as described byUS2003/0055270 is that the selectivity towards valerolactone is insufficient. Another problem of process as described byUS2003/0055270 is that the conversion yield is insufficient. The use of valerolactone in the production of adipic acid is environmentally advantageous since it can be produced from levulinic acid, which in turn can be produced from renewable sources such as plant waste. - Therefore, the invention provides a process for the preparation of valerolactone, said process comprising reacting levulinic acid with hydrogen by using a solid Ru catalyst, characterised in that the process is carried out in the presence of at least 0.08 % (w/w) water relative to the amount of levulinic acid.
- The amount of water is expressed relative to the amount of initial levulinic acid, i.e. the amount of levulinic acid at the start of the process when no or hardly any levulinic acid has been converted. The amount of levulinic acid can be determined e.g. by GC.
- The process of the invention involves a hydrogenation reaction. The Ru catalyst is preferably present in a catalytic amount and is suitable for hydrogenation of ketones. Preferably the Ru catalyst is supported on a support medium, for example on carbon or alumina. However, Ru oxide (RuO) can also be used.
- The inventors surprisingly found that reacting levulinic acid with hydrogen by using a solid Ru catalyst, whereby the process is carried out in the presence of at least 0.08% (w/w) water relative to the amount of levulinic acid, a high production capacity and/or a high conversion yield and/or a high selectivity may be realised in the production of valerolactone. In contrast, the conversion of levulinic acid to valerolactone using a solid Ru catalyst as carried out in
US2003/0055270 is done without the addition of any water. In fact, inUS2003/0055270 it is described that the catalyst is dried at 400°C for 2 hours prior to the process. - That reacting levulinic acid with hydrogen by using a solid Ru catalyst in the presence of at least 0.08% (w/w) water relative to the amount of levulinic acid results in high conversion yield and/or a high selectivity is all the more surprising since said reaction involves the production of condensation water. As the reaction proceeds, the amount of water in the process increases. Nevertheless, it appears that the condensation water which builds up during the course of the reaction does not impart the same effect with respect to reaction velocity and/or selectivity as does the initial presence of at least 0.08% w/w water, i.e. the initial presence of at least 0.08% w/w water in the process is essential.
- The amount of water in the process of the invention is preferably at least 0.1% w/w, more preferably at least 0.2%, at least 0.3%, at least 0.4% w/w, more preferably at least 0.5%, at least 0.75% w/w, more preferably at least 1%, at least 1.3%, at least 1.5% w/w, even more preferably at least 1,7%, at least 2%, at least 2.5% w/w, all relative to the amount of levulinic acid. The upper limit of the amount of water is less critical. However, if the amount of water is too high, the substrate and/or catalyst may be diluted such that the reaction velocity or productivity may decrease which is undesired. Therefore, the amount of water in the process of the invention is preferably less than 10% w/w, more preferably less than 8% w/w, less than 6% w/w, less than 5% w/w, all relative to the amount of levulinic acid.
- The water which is present in the process of invention may be added separately, or added as part of one or more of the components, or both. For example, it may be added to the process in the form of liquid water or in the form of steam. It may also be present in the form of crystal water. The water may also be added to process together with one or more of the reaction components, e.g. as part of the levulinic acid or the Ru catalyst or both. The water may also be added first and the other reaction components are added later. Reaction components such as levulinic acid and the catalyst may also be added first, and the water may be added subsequently. Other ways of adding water are also possible, such as first adding levulinic acid, then adding water, and subsequently adding the Ru catalyst, or first adding the Ru catalyst, then adding water and finally adding levulinic acid. If the catalyst and/or the levulinic acid happens to contain trace amounts of water, it may be preferred to first measure the water content of these reaction components, e.g. by Karl Fischer titration, such that the suitable amount of water to be added can be calculated in order to arrive at the desired water content in the process.
- The temperature at which the process of the invention is carried out is not critical and may be anywhere between 100 and 250°C, more preferably between 100 and 200°C. Preferably a temperature of between 100 and 150°C is used because it seems that the highest selectivity can be obtained in this temperature range. Lower temperatures are also desired due to cost considerations and equipment requirements.
- The pressure at which the process of the invention is carried out is also not critical, but it may be advantageous to carry out the process at lower pressure, e.g. less than 4.8 MPa. Preferably the pressure is between 1 and 4 MPa, more preferably between 1 and 3 MPa, even more preferably between 1 and 2.5 MPa, even more preferably between 1 and 2.2 MPa.
- The amount of catalyst to be used is not critical. Preferably the amount of catalyst is between 2.5 and 2,000 ppm Ru relative to the initial amount of levulinic acid present in the reaction mixture, i.e. the amount of levulinic acid which is present in the reaction mixture at the start of the reaction when no or hardly any levulinic acid has been converted. More preferably the amount of catalyst is between 5 and 1,000 ppm Ru, even more preferably between 10 and 500 ppm Ru, all relative to the initial amount of levulinic acid. The process of the invention may advantageously be done at low (e.g. less than 500 ppm Ru) catalyst concentrations whilst yielding good selectivity.
- The effect of at least 0.08% w/w water relative to the amount of levulinic acid may be stronger at lower amounts catalyst. In other words, the presence at least 0.08% w/w water relative to the amount of levulinic acid may be more important, and indeed may even be required for the hydrogenation reaction to proceed at all when a low amount of catalyst is selected, for instance for economic reasons.
- Ru catalysts such as Ru/C or Ru-Al2O3 are commercially available and the amount of Ru and any support are usually labeled. In case the amount of Ru is not given, the skilled person knows how to determine the amount of Ru, for example by atomic absorption spectrometry or plasma emission spectrometry.
- The process of the invention may be carried in the absence of a solvent. In the context of the invention a solvent is understood to be added to the reaction mixture, i.e. in the meaning of the invention the reaction product is not considered a solvent. The absence of a solvent may advantageously result in higher conversion and/or selectivity and may be preferred for economic reasons.
- The levulinic acid may be produced from renewable sources. A suitable example of renewable sources is plant material, particularly plant waste. Plant material usually contains carbohydrates that can serve as a starting molecule for the production of levulinic acid. For example, levulinic acid can be prepared by converting a C6 carbohydrate to levulinic acid in an acid-catalysed reaction. Such processes are for example described in
US3,065,263 ; B. Girisuta et al., Chem. Eng. Res. Des. 2006, 84, 339-349; B. F. M. Kuster et al., Carbohydr. Res., 1977, 54,165-176;WO89/10362 WO96/40609 - The invention may be particularly useful since it allows for economically feasible production of valerolactone, and also of derivatives thereof such as methylpentenoate, adipic acid dimethylester, adipic acid, hexamethylenediamine, and polyamide 6,6, all produced via or from renewable sources. One such a suitable renewable source is plant material, which can be converted into levulinic acid. Although the production of valerolactone from levulinic acid is known from
US2003/0055270 , the process conditions as described inUS2003/0055270 and/or conversion yield and/or selectivity resulting from said process may form a barrier for the economic feasibility of said process. The process ofUS2003/0055270 suffers from low conversion yield (usually less than 100%, often even less than 80% and even as low as 32%), low selectivity (less than 98.5%, occasionally even as low as 67.7%), is done at high process temperature (215°C) and high pressure (4.8 MPa), makes use of a solvent (dioxane) and high catalyst concentrations. For example, the amount of Ru/C used in Table 1 ofUS2003/0055270 typically ranges between 2% and 20% (w/w) relative to the amount of levulinic acid, which corresponds to a range of between approximately 1000 and 10,000 ppm Ru relative to the amount of levulinic acid, respectively. Low catalyst concentrations (such as for instance less than 1000 ppm Ru) are usually economically desirable, but the selectivity in the process as described inUS2003/0055270 appears to be lower at lower catalyst concentrations. Said barriers can be overcome by the process of the invention. - The invention further provides a process to produce methylpentenoate comprising converting valerolactone produced by the process of the invention into methylpentenoate by treatment with methanol in the presence of an acidic or basic catalyst. The conversion of valerolactone to methyl pentenoate can be done either in the liquid phase or in the gas phase, and is inter alia described in
WO 2005/058793 ,WO2004/007421 , andUS4,740,613 . - The invention also provides a process to prepare adipic acid dimethylester comprising converting methylpentenoate produced in the process of the invention by treatment with a catalyst, CO and methanol. Such an alkoxycarbonylation reaction is described by e.g.
W02001/068583 . - The invention also provides a process to prepare adipic acid comprising converting adipic acid dimethylester produced in the process of the invention to adipic acid in a hydrolysis reaction. The hydrolysis of adipic acid dimethylester to adipic acid is well known to the person skilled in the art. The hydrolysis is preferably catalysed by an acidic catalyst.
- The invention also provides a process to prepare ammonium adipate comprising converting adipic acid produced by the process of the invention to ammonium adipate by treatment with ammonia.
- The invention also provides a process to prepare adiponitrile comprising converting ammonium adipate produced in the process of the invention into adiponitrile in a dehydration reaction.
- The invention also provides a process to prepare hexamethylenediamine comprising converting adiponitrile produced of the process of the inventiont into hexamethylenediamine in a reduction reaction.
- The invention also provides a process to produce polyamide 6,6 by converting adipic acid, preferably adipic acid produced in a process according of the invention with hexamethylenediamine, preferably hexamethylenediamine produced by a process of the invention, in a polymerization reaction. Polyamide 6,6 produced by the invention, particularly polyamide 6,6 produced from adipic acid and hexamethylenediamine produced by a process of the invention may be advantageously environmentally sustainable.
- The invention will be further elucidated with reference to the following examples, without however being limited thereto.
- Levulinic acid was obtained from Acros Organics, Geel, Belgium. Valerolactone was measured by GC analysis using cyclohexylbenzene as an external standard. Escat 4401, CAS [7440-18-8] (reduced) containing 5% Ru/C (Ru:C ratio, 1:20) and 58.45% water, was purchased form Strem Chemicals, Newburyport, Massachusetts, USA. Dry Ru/C CAS [7440-18-8] containing 5% Ru/C (Ru:C 1:20) was also purchased from Strem Chemicals, Newburyport, Massachusetts, USA.
- A 150 mL autoclave (Parr Instrument Company, Moline, Illinois, USA) was charged with levulinic acid (80 g, 0.68 mol) and Ru/C catalyst (see Table 1). The ratio Ru:C in the catalyst was 1:20 based on dry weight. Water was added to the reaction mixture such as to obtain a total amount of water in the reaction mixture as shown in Table 1. The actual total water content was measured by means of Karl Fisher titration and is expressed as % (w/w) relative to the total weight of the reaction mixture. Then the autoclave was purged 3 times with nitrogen and subsequently 3 times with hydrogen. The autoclave was heated to 130°C and pressurized to 2.06 MPa hydrogen. Samples were taken in time. Results see Table 1.
Table 1. Results hydrogenation of levulinic acid to γ-valerolactone Entr y Catalyst Ru/C (mg) Total water content (wt %) Reaction time (h) Conversio n (%) Selectivity to VL (%) 1 Escat 4401 (58.45% water) 800 0.75 1 60 >99 2 Escat 4401 (58.45% water) 800 1.72 1 79 >99 3 Dry Ru/C 41.3 0.08 49.5 51 >99 4 Dry Ru/C 41.3 1.29 48 59 >99 5 Dry Ru/C 41.3 2.47 48 73 >99
Claims (16)
- Process for the preparation of γ-valerolactone, said process comprising reacting levulinic acid with hydrogen by using a solid Ru catalyst, characterised in that the process is carried out in the presence of at least 0.08 % (w/w) water relative to the amount of levulinic acid.
- Process of claim 1 wherein the amount of water in the reaction is at least 1% (w/w) relative to the amount of levulinic acid.
- Process of claim 1 or 2 wherein the amount of water in the reaction is at least 2.5% (w/w) relative to the amount of levulinic acid
- Process of any one of claim 1-3, wherein the reaction is carried out at a temperature of between 100 and 150°C.
- Process of any one of claim 1-4, wherein the reaction is carried out at a pressure of between 1 and 4 MPa.
- Process of any one of claim 1-5, wherein amount of Ru catalyst is between 10 and 500 ppm Ru relative to the amount of initial levulinic acid.
- Process of any one of claim 1-6, wherein said process is carried out in the absence of a solvent.
- Process of any one of claim 1-7 wherein levulinic acid is prepared by converting a C6 carbohydrate to levulinic acid in an acid-catalysed reaction.
- Process to prepare methylpentenoate comprising converting valerolactone produced by the process of any one of claim 1-8 into methylpentenoate by treatment with methanol in the presence of an acidic or basic catalyst.
- Process to prepare adipic acid dimethylester comprising converting methylpentenoate produced in the process of claim 9 by treatment with a catalyst, CO and methanol.
- Process to prepare adipic acid comprising converting adipic acid dimethylester produced in the process of claim 10 to adipic acid in a hydrolysis reaction.
- Process to prepare ammonium adipate comprising converting adipic acid produced by the process claim 11 into ammonium adipate by treatment with ammonia.
- Process to prepare adiponitrile comprising converting ammonium adipate produced in the process of claim 12 into adiponitrile in a dehydration reaction.
- Process to prepare hexamethylenediamine comprising converting adiponitrile produced of the process of claim 13 into hexamethylenediamine in a reduction reaction.
- Process to produce polyamide 6,6 by converting adipic acid produced in the process of claim 11 with hexamethylenediamine in a polymerization reaction.
- Process to produce polyamide 6,6 by converting adipic acid produced in the process of claim 11 with hexamethylenediamine produced by the process of claim 14 in a polymerization reaction.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL12172349T PL2537840T3 (en) | 2011-06-21 | 2012-06-18 | Process to produce valerolactone from levulinic acid |
EP12172349.8A EP2537840B1 (en) | 2011-06-21 | 2012-06-18 | Process to produce valerolactone from levulinic acid |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161499438P | 2011-06-21 | 2011-06-21 | |
EP11170809 | 2011-06-21 | ||
EP12172349.8A EP2537840B1 (en) | 2011-06-21 | 2012-06-18 | Process to produce valerolactone from levulinic acid |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2537840A1 EP2537840A1 (en) | 2012-12-26 |
EP2537840B1 true EP2537840B1 (en) | 2013-07-24 |
Family
ID=47220247
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12172349.8A Not-in-force EP2537840B1 (en) | 2011-06-21 | 2012-06-18 | Process to produce valerolactone from levulinic acid |
Country Status (10)
Country | Link |
---|---|
US (1) | US8598303B2 (en) |
EP (1) | EP2537840B1 (en) |
JP (1) | JP2014524905A (en) |
CN (1) | CN103619826B (en) |
BR (1) | BR102012015623B1 (en) |
CA (1) | CA2839137A1 (en) |
EA (1) | EA025474B1 (en) |
MY (1) | MY163070A (en) |
PL (1) | PL2537840T3 (en) |
WO (1) | WO2012175439A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3184517A1 (en) | 2015-12-23 | 2017-06-28 | Neste Oyj | A selective process for conversion of levulinic acid to gammavalerolactone |
US9884834B2 (en) | 2015-12-23 | 2018-02-06 | Neste Oyj | Combined levulinic acid and furfural production from biomass |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR088124A1 (en) * | 2011-04-01 | 2014-05-14 | Dsm Ip Assets Bv | PROCESS FOR THE PREPARATION OF ALCANOIC ACID ESTERS IN A CARBONILATION PROCESS USING PALADIO BIDENTED BIFOSPHATE BINDINGS |
WO2014150384A1 (en) * | 2013-03-15 | 2014-09-25 | Segetis, Inc. | Method of manufacture of octanedioic acid, precursors, and derivatives |
JP2018508485A (en) * | 2015-02-18 | 2018-03-29 | ディーエスエム アイピー アセッツ ビー.ブイ. | Continuous hydrogenation of levulinic acid |
KR20170118747A (en) | 2015-02-24 | 2017-10-25 | 디에스엠 아이피 어셋츠 비.브이. | Method for producing gamma valerolactone from levulinic acid |
US10377727B2 (en) | 2015-10-06 | 2019-08-13 | Synvina C.V. | Process for the preparation of gamma-valerolactone |
WO2017085986A1 (en) | 2015-11-16 | 2017-05-26 | 宇部興産株式会社 | Method for producing γ-valerolactone |
CN107824180A (en) * | 2017-08-25 | 2018-03-23 | 昆山普瑞凯纳米技术有限公司 | A kind of preparation method of load-type nanometer metal catalyst for levulic acid hydrogenation |
EP3830192A1 (en) * | 2018-08-01 | 2021-06-09 | Braskem America, Inc. | Thermoplastic compositions having improved toughness, articles therefrom and methods thereof |
CN113828339B (en) * | 2020-06-08 | 2023-08-29 | 中国石油大学(北京) | M-Co monoatomic alloy catalyst and preparation method and application thereof |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2368366A (en) * | 1942-08-21 | 1945-01-30 | Monsanto Chemicals | Process for the production of lactones |
US2786852A (en) * | 1953-08-19 | 1957-03-26 | Quaker Oats Co | Process of preparing gammavalerolactone |
GB896949A (en) * | 1957-12-14 | 1962-05-23 | Basf Ag | Improvements in the production of proto-anemonin and its homologues |
US3065263A (en) | 1959-11-17 | 1962-11-20 | Rayonier Inc | Process for the manufacture of levulinic acid |
NL8103173A (en) * | 1981-07-02 | 1983-02-01 | Stamicarbon | PROCESS FOR THE PREPARATION OF A 5-ALKYL-BUTYROLACTONE. |
DE3609139A1 (en) * | 1986-03-19 | 1987-09-24 | Basf Ag | METHOD FOR PRODUCING 4-PENTENIC ACID ESTERS |
US4897497A (en) * | 1988-04-26 | 1990-01-30 | Biofine Incorporated | Lignocellulose degradation to furfural and levulinic acid |
US5608105A (en) * | 1995-06-07 | 1997-03-04 | Biofine Incorporated | Production of levulinic acid from carbohydrate-containing materials |
US5883266A (en) * | 1998-01-16 | 1999-03-16 | Battelle Memorial Institute | Hydrogenated 5-carbon compound and method of making |
US6706912B2 (en) | 2000-03-14 | 2004-03-16 | Shell Oil Company | Process for the carbonylation of ethylenically unsaturated compounds |
BR0208248A (en) * | 2001-03-16 | 2004-03-02 | Du Pont | Process for preparing 5-methylbutyrolactone. |
US6835849B2 (en) * | 2002-07-15 | 2004-12-28 | E. I. Du Pont De Nemours And Company | Synthesis of alkenoate esters from lactones and alcohols |
US6946563B2 (en) * | 2003-06-16 | 2005-09-20 | E. I. Du Pont De Nemours And Company | Production of 5-methyl-dihydro-furan-2-one from levulinic acid in supercritical media |
EP1699750B1 (en) * | 2003-12-19 | 2013-11-06 | Shell Internationale Research Maatschappij B.V. | A process for the preparation of an alkyl alkenoate |
EP1828095B1 (en) * | 2004-12-23 | 2011-10-05 | Shell Internationale Research Maatschappij B.V. | A process for the hydrogenation of a lactone or of a carboxylic acid or an ester having a gamma-carbonyl group |
ATE493377T1 (en) * | 2007-05-22 | 2011-01-15 | Shell Int Research | METHOD FOR CONVERTING LEVULIC ACID INTO PENTORIC ACID |
CN101376650B (en) * | 2008-09-08 | 2013-04-03 | 中国科学技术大学 | Method for directly preparing gamma-valerolactone from acetylpropionic acid and aminic acid |
WO2010063742A1 (en) * | 2008-12-05 | 2010-06-10 | Basf Se | Method for producing delta valerolactone in the gas phase |
US8148553B2 (en) * | 2009-06-23 | 2012-04-03 | Wisconsin Alumni Research Foundation | Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities |
-
2012
- 2012-06-18 EP EP12172349.8A patent/EP2537840B1/en not_active Not-in-force
- 2012-06-18 CA CA2839137A patent/CA2839137A1/en not_active Abandoned
- 2012-06-18 JP JP2014516293A patent/JP2014524905A/en active Pending
- 2012-06-18 EA EA201400045A patent/EA025474B1/en not_active IP Right Cessation
- 2012-06-18 PL PL12172349T patent/PL2537840T3/en unknown
- 2012-06-18 CN CN201280031015.3A patent/CN103619826B/en not_active Expired - Fee Related
- 2012-06-18 WO PCT/EP2012/061558 patent/WO2012175439A1/en active Application Filing
- 2012-06-18 MY MYPI2013702344A patent/MY163070A/en unknown
- 2012-06-20 US US13/528,281 patent/US8598303B2/en not_active Expired - Fee Related
- 2012-06-25 BR BR102012015623-7A patent/BR102012015623B1/en not_active IP Right Cessation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3184517A1 (en) | 2015-12-23 | 2017-06-28 | Neste Oyj | A selective process for conversion of levulinic acid to gammavalerolactone |
US9884834B2 (en) | 2015-12-23 | 2018-02-06 | Neste Oyj | Combined levulinic acid and furfural production from biomass |
US9914714B2 (en) | 2015-12-23 | 2018-03-13 | Neste Oy J | Selective process for conversion of levulinic acid to gammavalerolactone |
Also Published As
Publication number | Publication date |
---|---|
CN103619826B (en) | 2015-09-23 |
PL2537840T3 (en) | 2013-12-31 |
CN103619826A (en) | 2014-03-05 |
MY163070A (en) | 2017-08-15 |
EA025474B1 (en) | 2016-12-30 |
EP2537840A1 (en) | 2012-12-26 |
BR102012015623B1 (en) | 2014-12-30 |
WO2012175439A1 (en) | 2012-12-27 |
US20120329981A1 (en) | 2012-12-27 |
CA2839137A1 (en) | 2012-12-27 |
US8598303B2 (en) | 2013-12-03 |
JP2014524905A (en) | 2014-09-25 |
EA201400045A1 (en) | 2014-05-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2537840B1 (en) | Process to produce valerolactone from levulinic acid | |
EP1828095B1 (en) | A process for the hydrogenation of a lactone or of a carboxylic acid or an ester having a gamma-carbonyl group | |
Mariscal et al. | Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels | |
US9969669B2 (en) | Method for producing muconic acids and furans from aldaric acids | |
EP2307395B1 (en) | Process for the oxidation of alcohol and/or aldehyde groups | |
KR20140113706A (en) | Process for production of hexamethylenediamine from 5-hydroxymethylfurfural | |
US20170001944A1 (en) | Chemical process to convert mucic acid to adipic acid | |
JP2009522350A5 (en) | ||
EP3333152A1 (en) | Deoxydehydration of sugar derivatives | |
JP2016512826A (en) | Method for producing dicarboxylic acids and derivatives from compositions containing ketocarboxylic acids | |
De Schouwer et al. | Metal-catalyzed reductive deamination of glutamic acid to bio-based dimethyl glutarate and methylamines | |
EP2573064B1 (en) | Process to produce alkenoic acid esters from lactones | |
FI127020B (en) | Selective method for the conversion of levulinic acid to gamma valerolactone | |
US20230028813A1 (en) | Processes for preparing aldaric, aldonic, and uronic acids | |
US9802910B2 (en) | Method for preparing 5-hydroxymethyl-2-furfural using acid catalyst in presence of ethylene glycol-based compound solvent derived from biomass | |
JP2020023572A (en) | Gamma-butyrolactone composition and manufacturing method therefor | |
Chen et al. | One pot synthesis of pharmaceutical intermediate 5-dimethylaminomethyl-2-furanmethanol from bio-derived carbohydrates | |
US9682912B2 (en) | Method for preparing levulinic acid using solid acid catalyst in presence of ethylene glycol-based compound solvent derived from biomass | |
CN105579441A (en) | Process for producing furan from furfural from biomass | |
KR101192576B1 (en) | Continuous Preparation Method for Furfural from Xylose | |
EP3415500B1 (en) | Method for preparing methylpyrrolidones | |
KR20160044775A (en) | Method of Preparing Anhydrosugar Alcohols under High Pressure | |
WO2012131028A1 (en) | Process to produce adipic acid and diesters thereof in a carbonylation process using palladium bidentate biphosphate ligands | |
WO2018065475A1 (en) | Method for the production of methylsuccinic acid and the anhydride thereof from citric acid | |
TW201249536A (en) | Process to produce adipic acid and diesters thereof in a carbonylation process using palladium bidentate biphosphate ligands |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
17P | Request for examination filed |
Effective date: 20120618 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C07D 307/33 20060101AFI20130117BHEP |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 623351 Country of ref document: AT Kind code of ref document: T Effective date: 20130815 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602012000159 Country of ref document: DE Effective date: 20130919 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 623351 Country of ref document: AT Kind code of ref document: T Effective date: 20130724 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131125 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131124 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130918 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131025 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20140425 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602012000159 Country of ref document: DE Effective date: 20140425 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602012000159 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140618 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602012000159 Country of ref document: DE Effective date: 20150101 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150227 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140618 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140630 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150630 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20120618 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160618 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160618 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20170411 Year of fee payment: 6 Ref country code: FI Payment date: 20170609 Year of fee payment: 6 Ref country code: IT Payment date: 20170619 Year of fee payment: 6 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20170726 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20130724 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180618 Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180619 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180618 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20190612 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180618 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20200701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200701 |